Bisisoindoline pigments

ABSTRACT

Novel bisisoindoline pigments of the formula (I) ##STR1## where the radicals A are identical or different radicals of a methylene-active compound, X is a divalent radical and the rings L are each unsubstituted or substituted, possess good fastness properties and are therefore suitable for a very wide range of applications, for example for pigmenting plastics, printing inks and surface coatings.

SUMMARY OF THE INVENTION

The present invention relates to bisisoindoline pigments of the formula(I) ##STR2## where the radicals A are identical or different radicals ofa methylene-active compound, X is a divalent radical and the rings L areeach unsubstituted or substituted.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The rings L are unsubstituted or monosubstituted, disubstituted,trisubstituted or tetrasubstituted, for example by halogen, preferablychlorine or bromine, C₁ -C₆ -alkyl, in particular methyl or ethyl, C₁-C₆ -alkoxy, such as methoxy or ethoxy, carboxyl, nitro and/or carbamyl.

The radicals A═ are of the formulae (II) to (VIb): ##STR3##

In formula (II), R¹ is a radical which activates the methylene group,eg. cyano; carbamyl which is unsubstituted or substituted by C₁ -C₆-alkyl, benzyl, naphthyl or phenyl, where phenyl, benzyl and naphthylmay be further substituted by, for example, chlorine, bromine, C₁ -C₆-alkyl, C₁ -C₆ -alkoxy, nitro, trifluoromethyl, C₁ -C₆ -alkylcarbonyl,in particular by acetyl, cyano, C₁ -C₆ -alkylamino, benzylamino,phthalimidyl, carbamyl or C₁ -C₆ -alkoxycarbonyl; C₁ -C₆ -alkylcarbonyl,preferably acetyl; benzoyl, C₁ -C₆ -alkoxycarbonyl, benzyloxycarbonyl orphenoxycarbonyl, benzoyl, benzyl and phenoxy being unsubstituted orsubstituted hy halogen, such as chlorine or bromine, nitro, C₁ -C₆-alkyl, C₂ -C₇ -alkanoylamino or phthalimidyl; phenyl which isunsubstituted or substituted by halogen, in particular chlorine orbromine, nitro, cyano or trifluoromethyl; or a heterocyclic radical ofthe formula ##STR4##

The ring M in formulae (VIIa) to (VIId) can be further substituted, forexample by halogen, such as chlorine or bromine, nitro, C₁ -C₆ -alkyland/or C₁ -C₆ -alkoxy, preferably by chlorine, bromine, methyl, ethyl,methoxy or ethoxy.

In formulae (III) to (VIb), the radicals R² independently of one anotherare each hydrogen or C₁ -C₆ -alkyl, or each phenyl which isunsubstituted or substituted by halogen, such as chlorine or bromine, C₁-C₆ -alkyl, C₁ -C₆ -alkoxy or nitro, or are each α- or β-naphthyl, R³ isC₁ -C₆ -alkyl, preferably methyl, amino, benzylamino, carbamyl or C₁ -C₆-alkoxycarbonyl, R⁴ is C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen,preferably chlorine, or nitro, p is 0, 1 or 2, Z is 0 or S, R⁵ ishydrogen or C₁ -C₆ -alkyl, preferably methyl, R⁶ is halogen, preferablychlorine, or nitro, and q is 0, 1, 2, 3 or 4.

Specific examples of suitable divalent radicals --X-- are: ##STR5## thebenzene and naphthalene rings being unsubstituted or substituted byhalogen, such as chlorine or bromine, nitro, C₁ -C₆ -alkyl and/or C₁ -C₆-alkoxy. The rings are preferably unsubstituted or substituted bychlorine, bromine, methyl, ethyl, methoxy and/or ethoxy.

Preferred bisisoindoline pigments are those of the formula (IX) ##STR6##where the radicals A¹ are identical or different radicals of the formula##STR7## R⁷ is cyano, carbamyl, C₁ -C₄ -alkylcarbamyl, phenylcarbamyl,the phenyl radical being unsubstituted or substituted by chlorine,bromine, C₁ -C₄ -alkyl, nitro, C₁ -C₄ -alkoxy or C₁ -C₄ -alkoxycarbonyl,##STR8## and M has the above meanings.

Particularly preferred bisisoindoline pigments are those of the formula(X) ##STR9## where the radicals A² are identical or different radicalsof the formula ##STR10## X² is 1,4- or 1,3-phenylene which isunsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, chlorineor bromine, and R⁸ is cyano, carbamyl, N-methylcarbamyl orN-ethylcarbamyl or is phenylcarbamyl which is substituted by chlorine,bromine, methyl, methoxy or carbomethoxy.

Of particular interest are the compounds of the formulae (I), (IX) and(X) in which both radicals A, A¹ or A² are identical.

Very particularly noteworthy bisisoindoline pigments are those of theformula (XI) ##STR11## where R⁹ is methyl or ethyl, R¹⁰ is methyl,ethyl, methoxy, ethoxy or chlorine and n is 0, 1 or 2, and, when n is 2,the radicals R¹⁰ may be identical or different.

Specific examples of C₁ -C₆ -alkyl are methyl, ethyl, n- and isopropyl,n- and isobutyl, but-2-yl, tertbutyl, pentyl, hexyl and2,2-dimethylbutyl, C₁ -C₄ -alkyl being preferred.

Examples of suitable C₁ -C₆ -alkoxy radicals are methoxy, ethoxy, n- andisopropoxy, n- and isobutoxy, pentyloxy and hexyloxy, C₁ -C₄ -alkoxybeing preferred and methoxy and ethoxy being particularly preferred.

The compounds of the formula (I) can, depending on the radical --X--(formulae (VIIIa) to (VIIIb)), be prepared by stepwise reaction of acompound of the formula ##STR12## with a diamine of the formula H₂N--X--NH₂ (XIII) or, in the case of the radicals X of the formulae(VIIIq) and (VIIIr), by reaction with a hydrazide of the correspondingdicarboxylic acid with elimination of ammonia.

Compounds (I) in which X is a radical of the formulae (VIIIt) to (VIIIv)can be obtained by stepwise reaction of a compound (XII) with thecorresponding diisocyanate.

Compounds of the formula (I) in which X is a radical of the formula(VIIlq), (VIIIr) or (VIIIs) are also obtainable by reacting a compoundof the formula ##STR13## with the corresponding terephthaloyl chloride,with oxalyl chloride or with the corresponding terephthalaldehyde.

The reactions are advantageously carried out in an inert organic solventat from 120° to 150° C., preferably from 50° to 120° C.

Suitable organic solvents are alcohols, such as methanol, ethanol, amylalcohol or glycol monoalkyl ethers, aromatic, such as chlorobenzene,nitrobenzene or toluene, amidic solvents, such as formamide,N,N-dimethylformamide or N-methylpyrrolidone, and acids, such as formicacid or acetic acid.

For the reactions with diisocyanates, aromatic hydrocarbons, such asxylene, toluene, chlorobenzene or nitrobenzene, or N,N-dimethylformamidecan be used.

Asymmetric compounds (I), ie. those in which the two radicals A aredifferent, are obtained by condensation of mixtures of the compounds ofthe formula (XII).

Such asymmetric compounds (I) can also be prepared by reacting acompound of the formula (XII) with a nitroamino compound H₂ N--X--NO₂(XIIIa) to give ##STR14## which is reduced to the corresponding aminocompound and then condensed with a further compound (XII) (in which theradical A differs from the radical A in the formula XV) to give theasymmetric compound (I).

The salts or complexes of the compounds of the formula (I) are preparedby conventional methods, for example by heating the compound with thecorresponding metal salt in N,N-dimethylformamide, N-methylpyrrolidoneor formamide at elevated temperatures (about 140° C.) for some time(about 5-10 hours).

The compounds of the formula (I) are obtained in a form suitable for useas a pigment, or can be converted to a suitable form by conventionalafter-treatment methods, for example by milling with or without millingassistants, such as inorganic salts, in the presence or absence of asolvent, such as toluene, xylene, dichlorobenzene orN-methylpyrrolidone. The color strength and transparency of the pigmentcan be influenced by varying the after-treatment.

The colorants of the formula (I) are lightfast and fast to migration andare therefore suitable for a very wide range of pigment applications.For example, they can be used for the preparation of very fast pigmentedsystems, such as mixtures with other substances, formulations, coatings,printing inks, colored paper and colored macromolecular substances.Mixtures with other substances may be, for example, mixtures withinorganic white pigments, such as titanium dioxide (rutile) or withcement. Formulations are, for example, flush pastes containing organicliquids or pastes and fine pastes with water, dispersants and, ifrequired, preservatives. The term coatings covers, for example,physically or oxidatively drying surface coatings, baking finishes,reactive coatings, two-component coatings, emulsion paints forweather-resistant coatings, and distempers. Printing inks are those usedfor printing paper, textiles and tin plate. The macro-molecularsubstances may be of natural origin, such as rubber, obtained bychemical modification, eg. cellulose acetate, cellulose butyrate orrayon, or produced synthetically, eg. polymers, polyadducts andpolycondensates. Examples are thermoplastic materials, such as polyvinylchloride, polyvinyl acetate, polyvinyl propionate, polyolefins, eg.polyethylene, nylons, nylon superpolymers, polymers and copolymers ofacrylates, methacrylates, acrylonitrile, acrylamide, butadiene andstyrene, and polyurethanes and polycarbonates. The substances pigmentedwith the claimed products may be in any form.

The pigments of the formula (I) are moreover very waterfast, oilfast,acidfast, limefast, alkalifast and solventfast, fast to overcoating,overspraying and sublimation, heat-resistant and resistant tovulcanization, have a very high color strength and are readilydispersible in plastic materials.

The Examples which follow illustrate the invention. Parts are by weight.

EXAMPLE 1

45 parts of 1-imino-3-(cyano-N-methylcarbamylmethylene)-isoindoline and11 parts of p-phenylenediamine in 700 parts of glacial acetic acid arestirred for 5 hours at 100° C. The mixture is cooled to 70° C. and thenfiltered, and the residue is washed with glacial acetic acid andmethanol and dried to give 47 parts of a compound of the formula##STR15## which, when incorporated into surface coatings, gives deep,lightfast, high-hiding brilliant orange colorations.

EXAMPLES 2-56

The procedure described in Example 1 is followed, except that, insteadof 1-imino-3-(cyano-N-methylcarbamylmethylene)-isoindoline andp-phenylenediamine, isoindoline compounds of the formula ##STR16## anddiamines of the formula

    H.sub.2 N--X--NH.sub.2                                     (XIII)

where A and --X-- have the meanings stated in the Table below, are used.The resulting pigments give colorations having the hues stated in column4 when incorporated into coatings, and have similar properties.

    __________________________________________________________________________    Example                                                                            A                    X                     Hue                           __________________________________________________________________________     2                                                                                  ##STR17##                                                                                          ##STR18##            yellow                         3   "                                                                                                   ##STR19##            yellow                         4   "                                                                                                   ##STR20##            red                            5   "                                                                                                   ##STR21##            red                            6   "                                                                                                   ##STR22##            yellow                         7                                                                                  ##STR23##                                                                                          ##STR24##            orange                         8   "                                                                                                   ##STR25##            yellow                         9                                                                                  ##STR26##                                                                                          ##STR27##            yellow                        10                                                                                  ##STR28##                                                                                          ##STR29##            yellow                        11   "                                                                                                   ##STR30##            yellow                        12                                                                                  ##STR31##                                                                                          ##STR32##            red                           13                                                                                  ##STR33##                                                                                          ##STR34##            red                           14   "                                                                                                   ##STR35##            red                           15   "                                                                                                   ##STR36##            red                           16   "                                                                                                   ##STR37##            red                           17   "                                                                                                   ##STR38##            maroon                        18                                                                                  ##STR39##                                                                                          ##STR40##            red                           19                                                                                  ##STR41##                                                                                          ##STR42##            orange                        20                                                                                  ##STR43##                                                                                          ##STR44##            yellow                        21                                                                                  ##STR45##                                                                                          ##STR46##            red                           22                                                                                  ##STR47##                                                                                          ##STR48##            maroon                        23                                                                                  ##STR49##                                                                                          ##STR50##            red                           24                                                                                  ##STR51##                                                                                          ##STR52##            yellow                        25                                                                                  ##STR53##                                                                                          ##STR54##            orange                        26   "                                                                                                   ##STR55##            orange                        27   "                                                                                                   ##STR56##            orange                        28   "                    NHCOCONH              yellow                        29   "                                                                                                   ##STR57##            yellow                        30   "                                                                                                   ##STR58##            yellow                        31   "                                                                                                   ##STR59##            yellow                        32                                                                                  ##STR60##                                                                                          ##STR61##            orange                        33                                                                                  ##STR62##                                                                                          ##STR63##            orange                        34                                                                                  ##STR64##                                                                                          ##STR65##            yellow                        35                                                                                  ##STR66##                                                                                          ##STR67##            orange                        36   "                                                                                                   ##STR68##            yellow                        37                                                                                  ##STR69##                                                                                          ##STR70##            orange                        38   "                                                                                                   ##STR71##            orange                        39                                                                                  ##STR72##                                                                                          ##STR73##            orange                        40                                                                                  ##STR74##                                                                                          ##STR75##            brown                         41                                                                                  ##STR76##                                                                                          ##STR77##            brown                         42                                                                                  ##STR78##                                                                                          ##STR79##            red                           43                                                                                  ##STR80##                                                                                          ##STR81##            red                           44                                                                                  ##STR82##                                                                                          ##STR83##            orange                        45                                                                                  ##STR84##                                                                                          ##STR85##            yellow                        46                                                                                  ##STR86##                                                                                          ##STR87##            yellow                        47                                                                                  ##STR88##                                                                                          ##STR89##            yellow                        48                                                                                  ##STR90##                                                                                          ##STR91##            yellow                        49                                                                                  ##STR92##                                                                                          ##STR93##            brown                         50                                                                                  ##STR94##                                                                                          ##STR95##            orange                        51                                                                                  ##STR96##                                                                                          ##STR97##            brown                         52                                                                                  ##STR98##                                                                                          ##STR99##            brown                         53                                                                                  ##STR100##                                                                                         ##STR101##           brown                         54                                                                                  ##STR102##                                                                                         ##STR103##           brown                         55                                                                                  ##STR104##                                                                                         ##STR105##           brown                         56                                                                                  ##STR106##                                                                                         ##STR107##           red                           __________________________________________________________________________

EXAMPLES 57 to 59

The procedure described in Example 1 is followed, except that, insteadof 1-imino-3-(cyano-N-methylcarbamylmethylene)-isoindoline, theisoindoline compounds stated in column 2 of the Table below are reactedwith p-phenylenediamine. The resulting pigments give colorations havingthe hues stated in column 3 when incorporated into coatings, and havesimilar properties.

    ______________________________________                                        Example     Isoindoline compound                                                                         Hue                                                ______________________________________                                        57                                                                                         ##STR108##    red                                                58                                                                                         ##STR109##    orange                                             59                                                                                         ##STR110##    yellow                                             ______________________________________                                    

EXAMPLE 60

45 parts of 1-imino-3-(cyano-N-methylcarbamylmethylene)-isoindoline and16 parts of p-phenylenediisocyanate in 600 parts of dimethylformamideare stirred for 5 hours at 150° C. The mixture is cooled to 70° C. andthen filtered, and the residue is washed with dimethylformamide andmethanol and dried to give 40 parts of a compound of the formula##STR111## which, when incorporated into coatings, gives deep,high-hiding red colorations possessing good fastness to migration.

EXAMPLES 61-67

The procedure of Example 60 is followed, except that, instead of1-imino-3-(cyano-N-methylcarbamylmethylene)-isoindoline and p-phenylenediisocyanate, isoindoline compounds of the formula XI and diisocyanatesof the formula

    O═C═N--X.sup.1 --N═C═O,

where A and X¹ have the meanings given in the Table below, are used. Thepigments color coatings in the hues stated in column 4. The pigmentproperties are similar to those of the pigment obtained as described inExample 60.

    __________________________________________________________________________     Example                                                                            A                                                                                              ##STR112##        Hue                                  __________________________________________________________________________    61                                                                                  ##STR113##                                                                                     ##STR114##       red                                   62                                                                                  ##STR115##      "                 brown                                 63                                                                                  ##STR116##      "                 orange                                64                                                                                  ##STR117##                                                                                     ##STR118##       brown                                 65                                                                                  ##STR119##                                                                                     ##STR120##       orange                                66   "                                                                                               ##STR121##       yellow                                67                                                                                  ##STR122##                                                                                     ##STR123##       red                                   __________________________________________________________________________

Examples of use

(a) Finish

10 parts of the colorant obtained as described in Example 1 and 95 partsof a baking finish mixture containing 70% of coconut alkyd resin(dissolved in xylene to give a 60% strength solution) and 30% ofmelamine resin (dissolved in butanol/xylene to give a solution of about55% strength) are milled in an attrition mill. After application, andbaking for 30 minutes at 120° C., orange full-shade coatings possessinggood lightfastness and fastness to overspraying are obtained. Mixing intitanium dioxide gives orange white reductions. If the colorantsdescribed in Examples 2 to 67 are used, coatings possessing similar huesand similar properties are obtained.

(b) Plastic

0.5 parts of the colorant obtained as described in Example 1 is appliedonto 100 parts of commodity grade polystyrene granules by tumbling, andthe colored granules are homogenized by extrusion at from 190° to 195°C. Lightfast orange extrudants are obtained. If a mixture consisting of0.5 part of colorant and 1 part of titanium dioxide is used, high-hidingorange colorations are obtained. If the pigments obtained as describedin Examples 2 to 67 are employed, similar colorations are obtained.

(c) Printing ink

8 parts of the pigment obtained as described in Example 1, 40 parts of arosin modified with phenol/formaldehyde, and from 55 to 65 parts oftoluene are mixed thoroughly in a dispersing unit. The resulting orangetoluene-based gravure printing ink gives lightfast prints. Similarresults are obtained if the colorants for Examples 2 to 67 are used.

We claim:
 1. A bisisoindoline pigment of the formula: ##STR124## whereinA= is a methylene-active radical of the formula ##STR125## the tworadicals A being identical or different, and R¹ is cyano; carbamyl whichis unsubstituted or substituted by C₁ -C₆ -alkyl, benzyl, naphthyl orphenyl, the three last mentioned radicals being unsubstituted orsubstituted by chlorine, bromine, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, nitro,trifluoromethyl, C₁ -C₆ -alkylcarbonyl, cyano, C₁ -C₆ -alkylamino,benzoylamino, phthalimidyl, carbamyl or C₁ -C₆ -alkoxycarbonyl; C₁ -C₆-alkylcarbonyl; benzoyl, C₁ -C₆ -alkoxycarbonyl, benzyloxycarbonyl orphenoxycarbonyl, where benzoyl, benzyl and phenoxy are unsubstituted orsubstituted by halogen, nitro, C₁ -C₆ -alkyl, C₂ -C₇ -alkanoylamino orphthalimidyl; phenyl which is unsubstituted or substituted by halogen,nitro, trifluoromethyl or cyano; or a heterocyclic radical of theformula ##STR126## where the rings M are each unsubstituted orsubstituted by halogen, nitro, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy; theradicals R² independently of one another are each hydrogen or C₁ -C₆-alkyl, or are each phenyl which is unsubstituted or substituted byhalogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, nitro, or are each α- orβ-naphthyl; R³ is C₁ -C₆ -alkyl, amino, benzoylamino, carbamyl or C₁ -C₆-alkoxycarbonyl; R⁴ is C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, halogen or nitro;R⁵ is hydrogen or C₁ -C₆ -alkyl; R⁶ is halogen or nitro; Z is O or S; pis 0, 1 or 2 and q is 0, 1, 2, 3 or 4,wherein --X-- is ##STR127## thebenzene and naphthalene rings being unsubstituted or substituted byhalogen, nitro, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy, and rings L aremonosubstituted, disubstituted, trisubstituted or tetrasubstituted byhalogen, C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, nitro or carbamyl.
 2. Abisisoindoline pigment as claimed in claim 1, wherein the two radicals Aare identical.
 3. A bisindoline pigment as claimed in claim 1, wherein--X-- is ##STR128## the benzene and naphthalene rings beingunsubstituted or substituted by halogen, nitro, C₁ -C₆ -alkyl or C₁ -C₆-alkoxy.
 4. A bisindoline pigment as claimed in claim 3, wherein --X--is ##STR129## the benzene and naphthalene rings being unsubstituted orsubstituted by halogen, nitro, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy.
 5. Abisisoindoline pigment as claimed in claim 1, wherein halogen ischlorine or bromine.
 6. A bisisoindoline pigment as claimed in claim 1,of the formula ##STR130## where the radicals A¹ are identical ordifferent radicals of the formula ##STR131## X¹ is ##STR132## R⁷ iscyano, carbamyl, C₁ -C₄ -alkylcarbamyl, phenylcarbamyl, the phenylradical being unsubstituted or substituted by chlorine, bromine, C₁ -C₄-alkyl, nitro, C₁ -C₄ -alkoxy or C₁ -C₄ -alkoxycarbonyl, ##STR133## andthe rings M are unsubstituted or substituted by chlorine, bromine,nitro, C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy.
 7. A bisisoindoline pigment asclaimed in claim 6, wherein the rings M are unsubstituted or substitutedby chlorine, bromine, methyl, ethyl, methoxy or ethoxy.
 8. Abisisoindoline pigment as claimed in claim 6, wherein the two radicalsA¹ are identical.
 9. A bisisoindoline pigment as claimed in claim 1, ofthe formula ##STR134## where the radicals A² are identical or differentradicals of the formula ##STR135## X² is 1,4- or 1,3-phenylene which isunsubstituted or substituted by methyl, ethyl, methoxy, ethoxy, chlorineor bromine, and R⁸ is cyano, carbamyl, N-methylcarbamyl orN-ethylcarbamyl or is phenylcarbamyl which is substituted by chlorine,bromine, methyl, methoxy or methoxycarbonyl.
 10. A bisisoindolinepigment as claimed in claim 9, wherein the two radicals A² areidentical.
 11. A bisisoindoline pigment as claimed in claim 1, of theformula ##STR136## where R⁹ is methyl or ethyl, R¹⁰ is methyl, ethyl,methoxy, ethoxy or chlorine and n is 0, 1 or 2, and, when n is 2, theradicals R¹⁰ are identical or different.